Rapid stabilization process for photographic silver halide materials

ABSTRACT

An improved stabilization process for photographic silver halide light-sensitive material comprising adding to a rinsing solution, used in the process, an antioxidant selected from the group recited in claim 1.

United States Patent Ohkubo et al.

[54] RAPID STABILIZATION PROCESS FOR PHOTOGRAPHIC SILVER HALIDE MATERIALS [72] Inventors: Kinji Ohkubo; Katsumi Hayashi, both of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd., Ashigara,

Kanagawa, Japan [22] Filed: Nov. 28, 1969 [21] Appl. No.: 880,975

[30] Foreign Application Priority Data Nov. 29, 1968 Japan ..43/87417 [52] US. Cl ..96/61, 96/50, 96/95 [51] Int. Cl .G03c 5/38, G030 5/26, G03c H06 [58] Field of Search ..96/61, 50, 48 OF, 95

[451 Mayl6, 1972 Primary Examiner-Norman G. Torchin Assistant ExaminerM. F. Kelley Attorney-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT An improved stabilization process for photographic silver halide light-sensitive material comprising adding to a rinsing solution, used in the process, an antioxidant selected from the group recited in claim 1.

12 Claims, No Drawings RAPID STABILIZATION PROCESS FOR PHOTOGRAPI'IIC SILVER HALIDE MATERIALS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rapid stabilization process for photographic light-sensitive silver halide materials.

2. Description of the Prior Art The conventional photographic processing of exposed photographic silver halide materials generally consists of four steps: development, stopping, fixing and washing. Since such photographic processing requires a considerable period of time, numerous attempts have been made to obtain photographic prints in a short access time.

One of the well-known methods proposed for the rapid processing of photographic silver halide material is a stabilization process. In the stabilization process, an exposed photographic material which has a silver halide emulsion layer coated on a support, is developed and treated with an aqueous solution (a stabilizing solution) containing a stabilizing agent, whereby the unexposed and undeveloped silver halides remaining in the photographic silver halide emulsion layer are converted into a silver complex which is stable to light and shows no change upon exposure to light. In this process, fixing is not required and thus the process reduces the time necessary for processing the exposed emulsion.

Various stabilizing agents have been described in the technical literature, e.g., I-I.D. Russell, E.C. Yackel and G. B. Bruce, PSA Journal Vol. 16, Section B, August 1950, pp. 59-62. The article discloses the use of alkali metal thiosulfates and ammonium thiocyanate, alkali metal thiocyanates, ammonium thiocyanate, alkali metal thiosulfates and ammonium thiosulfate as stabilizing agents.

The use of alkali metal thiocyanates or ammonium thiocyanate as a stabilizing agent has the advantage that the undeveloped light-sensitive silver halide remaining in the emulsion layer can be quickly converted into a light-stable or a light-insensitive silver thiocyanate complex. However, this process is attended by the disadvantage that the photographic silver halide material stabilized by the thiocyanate becomes sticky, which renders subsequent treatment of the stabilized print inconvenient. This phenomenon is thought to be caused by the fact that the alkali metal thiocyanates and the ammonium thiocyanate are deliquescent and have the property of softening gelatin which is used in the silver halide emulsion layer of the material as a binder. Moreover, as these stabilizing agents gradually oxidize the metallic silver of the stabilized print images to form the silver complex, the image density is reduced or the image may even disappear. Such a phenomenon is particularly likely to occur when the print is kept under high humidity conditions.

On the other hand, the use of alkali metal thiosulfates or ammonium thiosulfate has the advantage that the photographic silver halide materials stabilized by the thiosulfate exhibits no stickiness. This is thought to be caused by the fact that the alkali metal thiosulfates and ammonium thiosulfate are not deliquescent. Another advantage of using the alkali metal thiosulfates and the ammonium thiosulfate as a stabilizing agent is that the photographic silver halide materials stabilized by the thiosulfates are capable of being stored for long periods of time, as are conventionally processed prints, when the stabilized prints were washed with running water. This is because the silver thiosulfate complex salt formed by the reaction of the thiosulfate and the silver halide are so stable that they will not decompose during washing.

However, this process is attended by the disadvantage that when the photographic silver halide materials stabilized by the thiosulfate are stored under high humidity conditions, the white portions of the stabilized print discolor to yellow. This phenomenon is thought to be due to the following reason: since the stabilizing agent and the silver thiosulfate complex remaining in the stabilized prints are unstable, they are gradually decomposed during storage to form colored sulfides.

Furthermore, the stabilization process using the thiosulfate has the additional disadvantage that when the stabilized prints are stored under high humidity conditions, the color tone of the silver image changes from black to yellow (fading), whereby the density of the image is reduced. This phenomenon is thought to be due to the fact that the thiosulfate remaining in the stabilized prints forms silver sulfide by reacting with the developed silver.

In order to overcome the aforesaid drawbacks encountered in the stabilization process using alkali metal thiosulfates or ammonium thiosulfate as stabilizing agents, the following process is recommended in the aforesaid Russel et al. article. After developing an exposed photographic silver halide material in a developer and imbibing it in a stopping solution, the processed material is stabilized in a stabilizing solution containing 10 60 percent by weight sodium thiosulfate (stabilizer) and thereafter rinsed for 10 seconds in water or an aqueous solution of 10 percent Kodalk (registered trade name). Russell et al. state in their report: This post-stabilization treatment reduces the concentration of the stabilizer and the silver thiosulfate complexes and, in the case of the Kodalk solution, the print is rendered alkaline which further decreases the tendency to bleach and stain on moist incubation."

In U.S. Pat. No. 3,271,153, issued Sept. 6, 1966 to Eastman Kodak Company, a rapid development process for photographic silver halide materials is described, in which an exposed photographic silver halide material is developed with a silver halide developer, processed in a stabilizing solution containing silver halide solvent (e.g., sodium thiosulfate) to stabilize the unexposed silver halide, and further immersed in a post-stabilizing solution (rinsing solution) containing about 15 40 percent by weight of a mixture of monoand di-basic salts of phosphoric acid and about 2-20 percentby weight of a sulfite salt.

When a developed photographic silver halide material is first stabilized in a stabilizing solution containing alkali metal thiosulfates or ammonium thiosulfate, and thereafter processed in a rinsing solution containing an alkali metal sulfite, the following advantage is obtained as compared with the case of immersing the stabilized print in a rinsing solution containing no sulfite. That is, when the prints processed in a rinsing solution containing an alkali metal sulfite after stabilization are stored for a long period of time under high temperature and high humidity conditions, neither discoloring (fading) of the silver image to yellow nor the yellowing of the processed prints caused by the formation of colored sulfides occurs. These sulfides are formed by the decomposition of the remaining thiosulfates and the silver thiosulfate complex. These phenomena are thought to be due to the fact that the sulfite in the rinsing solution has the effect of preventing fading or discoloration of the silver image while also preventing the thiosulfate and the silver thiosulfate complex from being decomposed into sulfides.

The rinsing solution containing an alkali metal sulfite is also effective for the stabilization process using as the stabilizing agent an alkali metal thiocyanate salt or ammonium thiocyanate.

When a developed photographic silver halide material is stabilized in a stabilizing solution containing an alkali metal thiocyanate or ammonium thiocyanate and thereafter processed in a rinsing solution containing an alkali metal sulfite, the stickiness of the processed prints and fading (the lowering of image density) thereof can be remarkably reduced.

However, the use of an aqueous solution containing a sulfite salt as a rinsing solution causes the following problems: (1) When the rinsing solution containing a sulfite salt is filled in a processing bath and the bath is allowed to stand for a few days, the rinsing solution is degraded and the prints obtained by processing in the degraded rinsing solution are severely inferi or in keeping life. (2) When the rinsing solution containing a sulfite salt is, after preparation, stored in a bottle for a long period of time such as l or 2 years, a large amount of solid material crystallizes out.

These phenomena are considered to be caused by the oxidation of the sulfite.

As an antioxidant for an aqueous solution of a sulfite salt, dimethyl acetarnide, pyrogallol, resorcinol, hydroquinone, dimethylformamide, etc., are described in C. Schroctor, Sulfur Dioxide," page 55 (1966) published by Pergamon Press. However, although the antioxidation effect of dimethyl acetamide or dimethylformamide is effective in a diluted aqueous solution of about mole per liter of sulfite, such an effect is scarcely observed in a concentrated aqueous solution thereof of about O.252.5 moles per liter. Also, since other antioxidants such as pyrogallol, resorcinol, and hydroquinone are very strong reducing agents, the antioxidant is readily oxidized and hence their antioxidizing effect is lost after about 10 hours. Furthermore, since the oxidation products of pyrogallol, resorcinol and hydroquinone are red-brown in color, the white portions of the print processed in the rinsing solution containing such an antioxidant are stained or contaminated.

lt is, therefore, an object of the present invention to provide an improved rapid process for stabilizing photographic silver halide materials.

Another object is to provide an improved composition for the rinsing solution which has excellent tray life.

An additional object is to provide a method of preventing stain in rapidly processed photographic materials.

SUMMARY OF THE INVENTION According to the present invention, there is provided a rapid stabilization process for a photographic silver halide material comprising exposing the developer-containing photo graphic silver halide material, developing it in an activator, stabilizing it in a stabilizing solution containing a stabilizing agent, and rinsing the material in a rinsing solution containing a sulfite salt, in which is incorporated at least one of the following antioxidants: toluhydroquinone, chlorohydroquinone, nitrohydroquinone, 2-ben2ylthiotoluhydroquinone, N,N- dimethyl-p-phenylenediamine, 4-amino-3-methyl-N,N- diethylaniline, 4-amino-N-ethyl-N-(fl-hydroxyethyl) aniline, O- and p-aminophenols, N-(p-hydroxyphenyl)glycine, o-oxyp-aminophenol, p-aminosalicylic acid, 4-amino-N-methyl-N- butylaniline, 4-phenyl-aminoaniline, 4-sulfoethylaminophenol, 4-amino-N-ethyl-N-(B- aminoethyl)aniline, 4-(ethyl-B-methylarninoethyl) aminoaniline, 4-amino-benzylaniline, 4(4'-hydroxyphenyl) aminophenol, 4-(2'-Carboxyphenyl)aminophenol, 4-(2-sulfophenyl)aminoaniline, 4-(2'-sulfo-4'-aminophenyl)aminoaniline, 4-(4'-dirnethylaminophenyl)aminoaniline, 4- (3methylphenyl) aminoaniline, 4-(2'-chlorophenyl)aminoaniline, 2-pentylhydro-quinone, phenyl catechol, pyrogallol monomethyl ether, protocatechuic acid methyl ester, and sodium 1-amino-2-hydroxynaphthalene-6-sulfonate.

DETAILED DESCRlPIlON OF THE PREFERRED EMBODIMENTS The amount of the above mentioned antioxidant to be added is generally from 0.05 to 5 g./liter, preferably from 0.5 to 3 g./liter of the rinsing solution. The antioxidant may be added as a solution in water, a lower alcohol such as methanol, ethanol, isopropanol, etc., acetone, dioxane or the like.

As the sulfite salt used in the rinsing solution, sodium sultite, potassium sulfite, sodium bisulfite, potassium bisulfite and sodium metabisulfite may be employedv The concentration of the sulfite salt is in the range of from about to 200 grams per liter of the rinsing solution.

Furthermore, as shown in Example 1, in order to prevent the white portions of the processed print from being stained by the formation of oxidation products of a developing agent remaining in a silver halide emulsion layer after processing a photographic silver halide material having the developing agent in the emulsion layer, it is necessary that the pH of the rinsing solution be less than about 9.

cntn

In a rapid photographic process, it is desirable to omit the stopping step following development in order to reduce the access time. Accordingly, the stabilizing solution must have an acidity which is sufficient to stop the development. Thus, for preventing the lowering of the pH of the rinsing solution by the carriage of the stabilizing solution attached to the surface of the sensitive material subjected to the stabilizing processing, it is preferable to incorporate a suitable amount of water-soluble compound which is known as a pH buffer into the rinsing solution, so that the rinsing solution is endowed with a buffer action. The following compounds are effective as pH buffers in this invention; boric acid, borax, monosodium hydrogen phosphate, disodium hydrogen phosphate, monopotassium hydrogen phosphate, dipotassiurn hydrogen phosphate, sodium acetate, citric acid, sodium citrate, and ammonium citrate.

The invention will be further illustrated by reference to the following examples.

EXAMPLE 1 An emulsion was prepared by adding 20 grams of hydroquinone to l kilogram of a gelatino silver chloride emulsion (silver chloride43 percent by weight) and adjusting the pH ofthe mixture to 5.0. The emulsion thus prepared was then coated on a baryta-coated paper.

The photographic printing paper thus prepared was exposed and developed for 4 seconds at 25 C. in an activator having the following composition:

Activator Sodium hydroxide 30 g. Anhydrous sodium sulfite 40 g. Potassium bromide 5 g. Water to make 1 liter Thereafter, the photographic printing paper was processed for 20 seconds at 25 C. in a stabilizing solution having the following composition:

Stabilizing solution Anhydrous sodium sulfite 18 g. Boric acid 5 g. Ammonium thiosulfate g. Glacial acetic acid 45 ml. Water to make 1 liter The photographic printing paper thus stabilized was further processed for 20 seconds at 25 C. in a rinsing solution having the following composition:

Rinsing solution Sodium acetate 14 g. Boric acid 6 g. Sodium bisulfite g. p-Aminophenol 0.07 g. Water to make I liter The print thus obtained showed sufficient stability to light after drying.

The advantageous effect of the addition of the aforesaid compound, i.e., p-aminophenol in this example, to the rinsing solution was confirmed by the following experiment. One liter of each of (1) the above rinsing solution and (2) a control solution prepared by omitting p-aminophenol from the above described rinsing solution was placed in a bath and they were allowed to stand for 3 days while exposing the surface of the solution to air, and thereafter the concentration of sodium bisultite in the solutions was determined analytically. The photographic printing paper was exposed, developed in the above-described activator solution and stabilized in the abovedescribed stabilizing solution and thereafter rinsed in the aerated rinsing solutions. The prints thus obtained were stored for 20 hours under high temperature and high humidity conditions of 50 C. and 80 percent relative humidity, respectively, and thereafter the fading of the silver image and the contamination of the background of the print were measured, the results of which are shown in the following table.

TABLEI Rinsing Soln. Concentration of maximum Contamination sodium bisulfite density of of background after allowing to image stand Control soln. 80 g./liter 0.9 1.0

p-aminophenolcontaining soln. 178 g./liter 1.8 0.0

Note: Reflective density;

(") Reflective density measured at 436 m EXAMPLE 2 The photographic printing paper described in Example 1 was exposed and developed for 4 seconds at 25 C. in an activator having the following composition:

Activator Potassium hydroxide 30 g. Anhydrous sodium sulfite 40 g. Potassium bromide 5 g. Water to make 1 liter Then, the photographic printing paper was processed for seconds at C. in a stabilizing solution having the following composition:

Stabilizing solution Anhydrous sodium sulfite 18 g. Boric acid 5 g. Ammonium thiosulfate I50 g. Glacial acetic acid 45 ml. Water to make 1 liter Furthermore, the photographic printing paper was processed for 20 seconds at 25 C. in a rinsing solution having the following composition:

Rinsing solution Citric acid 21 g. Sodium citrate g. Anhydrous sodium sulfite 200 g. N,N-Dimethyl-p-phenylene diamine hydrochloride 0.2 g. Water to make 1 liter The print thus obtained showed sufficient stability to light after drying.

The advantageous effect of incorporating the compound of this invention, i.e., N,N-dimethyl-p-phenylene-diamine hydrochloride, to the rinsing solution was confirmed by the following experiment.

One liter of each of( l the above-described rinsing solution and (2) a control solution prepared by omitting N,N-dimethylp-phenylenediamine from the above-described rinsing solution, was placed in a bath and allowed to stand for 3 days while exposing the surface of the solutions to air, and thereafter the amount of the sodium sulfite in the rinsing solutions was determined. The photographic printing paper was exposed, developed in the above-described activator solution, stabilized in the above-described stabilizing solution, and then processed in the rinsing solutions thus aerated. The photographic prints thus obtained were stored under high temperature and high humidity conditions of 5O C. and 80 percent relative humidity, respectively, for 20 hours and then the fading of the silver image and the contamination of the background of the print were measured, the results of which are shown in the following table.

TABLE II Rinsing Soln. Concentration of Maximum Contamination sodium sulfite in density of of backthe rinsing soln. image* ground Control soln. g./liter 1.0 0.8

phenylenediamine g./liter 1.7 0.0

hydrochloridecontaining soln.

NOTE: Reflective density t") Reflective density measured at 436 my.

EXAMPLE 3 An emulsion was prepared by adding 25 grams of hydroquinone and 2.5 g. of lphenyl-3pyrazolidone to 1 kilogram of a gelatino silver chlorobromide emulsion and adjusting the pH of the mixture to 5.0. The resulting emulsion was applied to a barytacoated paper to obtain a photographic printing paper.

The photographic printing paper thus prepared was exposed and developed for 2 seconds at 25 C. in an activator having the following composition:

Activator Sodium hydroxide 55 g. Anhydrous sodium sultite 30 g. Potassium bromide 0.5 g. Water to make I liter The photographic printing paper was then processed for 20 seconds at 25 C. in a stabilizing solution having the following composition:

Stabilizing solution Anhydrous sodium sulfite 20 g. Sodium thiosulfate 120 g. Glacial acetic acid 20 ml. Water to make 1 liter Thereafter, the photographic printing paper was processed for 30 seconds at 25 C. in a rinsing solution having the following composition:

Rinsing solution Sodium monohydrogen phosphate 15 g. Sodium dihydrogen phosphate l2 g. Potassium sulfite 50 g. N-methyl-p-aminophenol sulfate 3 g. Water to make I liter The print thus obtained showed sufficient stability to light after drying.

The advantageous effect of the addition of the compound of this invention, i.e., N-methyl-p-aminophenol sulfate, to the rinsing solution was confirmed by the following experiment.

One liter of each of l) the above-described rinsing solution and (2) a control solution prepared by omitting N-methyl-paminophenol sulfate from the above-described rinsing solution composition was placed in a bath and allowed to stand for 3 days while exposing the surface of the solution to air. Thereafter, the concentration of potassium sulfite in the rinsing solutions was determined. The photographic printing paper was exposed, developed in the above-described activator, stabilized in the above-described stabilizing solution and thereafter processed in the rinsing solution thus aerated. The prints thus obtained were placed for 20 hours under high temperature and high humidity conditions of 50 C. and 80 percent relative humidity, respectively, and then the fading of the silver image and the contamination of the background of the print were measured, the results being shown in the following table.

TABLE III The photographic gelatino silver chlorobromide emulsion prepared by the procedure described in Example 3 was applied to a baryta-coated paper to provide a photographic printing paper.

After exposure, the printing paper thus prepared was developed for 2 seconds at 25 C. in an activator having the following composition:

Activator Sodium hydroxide 55 g. Anhydrous sodium sulfite 30 g. Potassium bromide 0.5 g. Water to make l liter The photographic printing paper was then processed for 7 seconds at 25 C. in a stabilizing solution having the following composition:

Stabilizing solution Ammonium thiocyanate 300 g. Sodium dihydrogen phosphate 10 g. Sodium monohydrogen phosphate g. Potassium pyrobisulfite 20 g. Cobalt sulfate heptahydrate 0.3 g l-Phenyl-5-mercaptotetrazole (0.1% methanol solution) 20 ml Water to make 1 liter The photographic printing paper was then processed for 5 seconds at C. in a rinsing solution having the following composition:

Rinsing solution Borax l g. Potassium monohydrogen phosphate 4.5 g. Potassium dihydrogen phosphate 10 g. Potassium metabisulfite 250 g. Toluhydroquinone l.0 g.

Water to make 1 liter The print thus obtained showed sufficient stability to light after drying.

The advantageous effect of the addition of the compound of this invention, i.e., toluhydroquinone, to the rinsing solution was confirmed by the following experiment.

One liter of each of the l) above-described rinsing solution and (2) a control solution prepared by omitting toluhydroquinone from the above-described rinsing solution was placed in a bath and allowed to stand for 3 days while exposing the solution to air. Thereafter, the concentration of potassium metabisulfite in the rinsing solution was determined. The photographic printing paper was exposed, developed, and stabilized as above, and then processed in the rinsing solution thus aerated.

The prints thus obtained were placed for 20 hours under high temperature and high humidity conditions of 50 C. and percent relative humidity, respectively, and thereafter the fading of the silver images and the contamination of the background of the print were measured. The results are shown in the following table.

TABLE IV Rinsing soln. Concentration of Maximum Contamipotassium metadensity nation of bisulfite of image background Control soln. gJliter 0.8 0.9 Toluhydroquinone-containing soln. 240 g./liter 1.9 0.0

Note: Reflective density ("N Reflective density measured at 476 mu.

Moreover, the print thus processed with the abovedescribed rinsing solution was extremely less sticky as compared with prints subjected to no further treatment following the stabilization.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variation and modification can be effected within the scope and spirit of the invention as described hereinabove and as defined in the appended claims.

What is claimed is:

1. In a rapid stabilization process for a photographic silver halide light-sensitive material comprising exposing a developer containing photographic silver halide material, developing said silver halide material in an activator solution. stabilizing said material in a stabilizing solution containing a stabilizing agent, and rinsing said material in a rinsing solution consisting essentially of an alkali metal sulfite and an antioxidant wherein the improvement comprises the antioxidant being selected from the group consisting of toluhydroquinone, chlorohydroquinone, nitrohydroquinone, Z-benzylthiotoluhydroquinone, N,N-dimethyl-p-phenylenediamine, 4-amino- 3-methyl-n,n-diethyl-aniline, 4-amino-N-ethyl-N-(B-hydroxyethyl)aniline, o-amino-phenol, p-aminophenol, N-(p-hydroxyphenyl)glycine, o-oxy-aminophenol, N-(p-hydroxyphenyl)- N-methylglycine, N-methyl-p-aminophenol, p-aminosalicylic acid, 4-amino-N-methyl-N-butylaniline, 4-phenylaminoaniline, 4-sulfoethylaminophenol, 4-amino-N-ethyl-N- (B-aminoethyhaniline, 4-(ethyl-B- methylaminoethyl)aminoaniline, 4-aminobenzylaniline, 4-(4'- hydroxydiphenyl )aminophenol, 4-( 2 '-sulfophenyl)aminophenol, 4-(2'carboxyphenyl) aminophenol, 4-(2- sulfophenyl )aminoaniline, 4-( 2 -sulfo-4 '-aminophenol aminoaniline, 4-(4'-dimethylaminophenyl)aminoaniline, 4- 3 '-methylphenyl )aminoaniline, 4-( 2 '-chlorophenyl)aminoaniline, 2-pentylhydroquinone, phenyl catechol, pyrogallol monomethyl ether, protocatechuic acid methyl ester, and sodium l-amino-hydroxynaphthalene-o-sulfonate,

said antioxidant being present in an amount of from 0.05 to 5.0 grams per liter of said rinsing solution, and the pH of said rinsing solution being less than 9 .0.

2. The rapid stabilization process as in claim 1, wherein the concentration of said antioxidant in said rinsing solution is from 0.5 to 3 g. per liter of said rinsing solution.

3. The rapid stabilization process as in claim 1 wherein said rinsing solution further contains at least one member selected from the group consisting of boric acid, borax, sodium hydrogen phosphate, disodium hydrogen phosphate, potassium hydrogen phosphate, dipotassium hydrogen phosphate, sodium acetate, citric acid, sodium citrate, and ammonium citrate.

4. The rapid stabilization process as in claim 1 wherein said alkali metal sulfite is sodium sulfite.

10. The process of claim 1, wherein said sulfite is present in an amount of from 20.0 to 200 grams per liter of rinsing solution.

11. The process of claim 1, wherein said antioxidant is added as a solution in a member selected from the group consisting of water, a lower alcohol, acetone, and dioxane.

12. The process of claim 11, wherein said lower alcohol is a member selected from the group consisting of methanol, ethanol, and isopropanol. 

2. The rapid stabilization process as in claim 1, wherein the concentration of said antioxidant in said rinsing solution is from 0.5 to 3 g. per liter of said rinsing solution.
 3. The rapid stabilization process as in claim 1 wherein said rinsing solution further contains at least one member selected from the group consisting of boric acid, borax, sodium hydrogen phosphate, disodium hydrogen phosphate, potassium hydrogen phosphate, dipotassium hydrogen phosphate, sodium acetate, citric acid, sodium citrate, and ammonium citrate.
 4. The rapid stabilization process as in claim 1 wherein said alkali metal sulfite is sodium sulfite.
 5. The rapid stabilization process as in claim 1 wherein said alkali metal sulfite is potassium sulfite.
 6. The rapid stabilization process as in claim 1 wherein said alkali metal sulfite is sodium bisulfite.
 7. The rapid stabilization process as in claim 1 wherein said alkali metal sulfite is potassium bisulfite.
 8. The rapid stabilization process as in claim 1 wherein said alkali metal sulfite is sodium metabisulfite.
 9. The rapid stabilization process as in claim 1 wherein said alkali metal sulfite is potassium metabisulfite.
 10. The process of claim 1, wherein said sulfite is present in an amount of from 20.0 to 200 grams per liTer of rinsing solution.
 11. The process of claim 1, wherein said antioxidant is added as a solution in a member selected from the group consisting of water, a lower alcohol, acetone, and dioxane.
 12. The process of claim 11, wherein said lower alcohol is a member selected from the group consisting of methanol, ethanol, and isopropanol. 